Properly quantified performance of a solar-thermal cavity receiver must not only account for the energy gains and losses as dictated by the First Law of thermodynamics, but it must also account for the quality of that energy. However, energy quality can only be determined from the Second Law. An equation for the Second Law efficiency of a cavity receiver is derived from the definition of available energy, which is a thermodynamic property that measures the maximum amount of work obtainable when a system is allowed to come into unrestrained equilibrium with the surrounding environment. The fundamental concepts of the entropy and availability of radiation were explored from which a workable relationship among the reflected cone half-angle, the insolation, and the concentrator geometric characteristics was developed as part of the derivation of the Second Law efficiency. First and Second Law efficiencies were compared for data collected from two receivers that were designed for different purposes. A Second Law approach to quantifying the performance of a solar-thermal cavity receiver lends greater insight into the total performance than does the conventional First Law method.